US5459112A - Reaction-bonded silicon carbide refractory product - Google Patents

Reaction-bonded silicon carbide refractory product Download PDF

Info

Publication number
US5459112A
US5459112A US08/306,087 US30608794A US5459112A US 5459112 A US5459112 A US 5459112A US 30608794 A US30608794 A US 30608794A US 5459112 A US5459112 A US 5459112A
Authority
US
United States
Prior art keywords
silicon carbide
reaction
article
silicon
refractory
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US08/306,087
Other languages
English (en)
Inventor
Baek H. Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unifrax 1 LLC
Original Assignee
Carborundum Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Carborundum Co filed Critical Carborundum Co
Assigned to CARBORUNDUM COMPANY, THE reassignment CARBORUNDUM COMPANY, THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIM, BAEK H.
Priority to US08/306,087 priority Critical patent/US5459112A/en
Priority to US08/450,596 priority patent/US5563108A/en
Priority to US08/450,447 priority patent/US5504046A/en
Priority to ZA957073A priority patent/ZA957073B/xx
Priority to JP51020496A priority patent/JP3311755B2/ja
Priority to DK95930968T priority patent/DK0783467T3/da
Priority to DE69516703T priority patent/DE69516703T2/de
Priority to ES95930968T priority patent/ES2148551T3/es
Priority to EP95930968A priority patent/EP0783467B1/en
Priority to AU34163/95A priority patent/AU701442B2/en
Priority to CA002199394A priority patent/CA2199394A1/en
Priority to KR1019970700768A priority patent/KR100386364B1/ko
Priority to BR9509007A priority patent/BR9509007A/pt
Priority to PCT/US1995/010858 priority patent/WO1996008450A1/en
Publication of US5459112A publication Critical patent/US5459112A/en
Application granted granted Critical
Priority to GR20000401784T priority patent/GR3034089T3/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/591—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by reaction sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/597—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon oxynitride, e.g. SIALONS

Definitions

  • This invention is in the field of refractory products, especially silicon carbide refractories; more particularly, this invention relates to reaction-bonded silicon carbide refractory articles in which the bond phase contains appreciable amounts of both silicon oxynitride and alumina.
  • Silicon carbide is well known for its high strength, hardness and abrasion resistance. Consequently, it is employed in many applications requiring these properties. Some of the applications in which hardness and abrasion resistance are critical include cyclone separators for mineral processing, burner liners for particulate coal-fired electric power plants, etc. Although these products and processes could probably utilize substantially pure silicon carbide, such products are not available in all the shapes and sizes of interest and are difficult and expensive to produce. Consequently, for many applications, reaction-bonded silicon carbide is employed.
  • Reaction-bonded silicon carbide comprises a discontinuous silicon carbide grain phase held together within a continuous bond phase matrix produced in situ from the reactants.
  • Bond phases typically found in reaction-bonded silicon carbide include, e.g., silicon nitride, silicon oxynitride and SiAlON.
  • Silicon carbide bonded with silicon nitride, Si 3 N 4 yields refractory articles with good abrasion-resistance, and such products have been commercially available for a number of years.
  • U.S. Pat. No. 2,152,258 discloses the use of silicon nitride as the bond phase for silicon carbide.
  • the silicon carbide grain is held together by intimately mixing it with silicon metal powder and water to produce a mixture moldable into a green body, and then firing the shaped green body in a non-oxidizing, nitrogenous atmosphere at the temperature and for the period of time necessary to convert substantially all the silicon metal to silicon nitride.
  • U.S. Pat. No. 2,618,565, U.S. Pat. No. 2,636,828 and U.S. Pat. No. 3,206,318 disclose the use of a fluoride, iron powder, vanadium metal or compounds containing vanadium, respectively, as a catalyst for the conversion of silicon metal to silicon nitride in the nitridation reaction.
  • U.S. Pat. No. 4,990,469 describes the production of a silicon nitride-bonded silicon carbide by nitriding a slip castable mixture of silicon carbide, silicon, alumina and iron oxide.
  • the nitridation reaction between silicon metal, which is a solid at the usual firing temperature, and gaseous nitrogen is heterogeneous, in that the reactants are in separate phases, and the rate of reaction can be determined by the rate of nitrogen diffusion or transport into the solid. Consequently, the composition and physical properties of the reaction-bonded product may be expected to depend to some extent upon variables such as the particle size of the silicon carbide and the porosity of the green body.
  • the heterogeneous nitridation reaction can also be employed to yield bond phases other than silicon nitride.
  • reaction-bonded silicon carbide in which the major component of the bond phase is silicon oxynitride, Si 2 ON 2 is produced by nitriding a mixture including particulate silicon carbide, silicon metal powder, and an oxygen source.
  • the resultant refractory articles have very good abrasion resistance. These products are available from The Carborundum Company, Niagara Falls, N.Y., as CAST REFRAX® refractories.
  • SiAlON is yet another bond phase which is useful for making reaction-bonded silicon carbide with good abrasion resistance.
  • SiAlON is an acronym coined to represent the stable solid solutions which result from the replacement of silicon and nitrogen atoms in compounds such as silicon nitride and silicon oxynitride with aluminum and oxygen atoms, respectively. Since some, but not all the silicon and nitrogen atoms are replaced, SiAlON represents, not a single substance, but a range of compositions representing different degrees of replacement.
  • ⁇ '-SiAlON is obtained from ⁇ -silicon nitride, O'-SiAlON from silicon oxynitride.
  • SiAlON-bonded silicon carbide can be produced by nitriding a mixture of silicon carbide grain, silicon, an aluminum source, and an oxygen source.
  • U.S. Pat. Nos. 4,243,621; 4,578,363 and 5,302,329 disclose the production of ⁇ '-SiAlON-bonded silicon carbide.
  • U.S. Pat. No. 4,506,021 discloses O-'-SiAlON ceramic products.
  • reaction-bonded silicon carbide articles including those commercially available, have properties which can depend upon, not only the chemical composition, but also upon the method of fabrication, the particle size distribution in the raw batch, and the porosity of the green body, unless the green body is quite thin.
  • the properties of the ceramic body are believed to be primarily the result of the fact the rate-determining step in the nitridation reaction is the rate of nitrogen gas diffusion into the green body, as pointed out above.
  • Chemical kinetics, rather than thermodynamics is known to control the outcome of many heterogeneous chemical reactions. On this basis, the following is offered as a nonbinding explanation of how this affects the products obtained from heterogeneous nitridation processes.
  • the nitriding reaction proceeds from the surface to the interior core of a green body as firing is initiated and continued. This progression is thought to require diffusion of nitrogen gas through voids or pores in the green body, i.e., diffusion and reaction rate depend upon the porosity of the green body. As the nitridation proceeds inward from the surface of the green body, some of the pores near the surface probably become nitrided but remain filled with nitrogen atoms whose progress further into the interior is then blocked by the nitridation products. Thus, the number of voids available for further nitrogen infiltration, diffusion and nitridation decreases.
  • the rate of reaction is reduced, and there is most likely unreacted silicon left proceeding from the surface further into the body. This is especially evident in cases in which the green body has a low amount of porosity to start with, particularly at the surface.
  • the nitridation reaction is exothermic, which introduces additional complications affecting both the nitrogen diffusion rate and the inherent rate of the nitridation reaction.
  • the gradation in nitridation from the surface into the core of the article becomes even more significant if a plaster mold is used to produce the green body from a slip or other water-containing raw batch.
  • Cast green bodies yield fired articles which are more dense, i.e., less porous, at the surface which contacts the plaster than in the core, because of the capillary action of the plaster at the surface.
  • the plaster tends to draw the water out of the surface first, and transport of water from the interior to the surface to restore equilibrium is impeded in the solid green body. Evaporation of the residual water when the green body is dried and fired leads to additional pores.
  • the lower porosity at the surface of the green body impedes diffusion of nitrogen gas into the body, retards the nitridation reaction, and causes a surface "skin" to be present on the fired reaction-bonded silicon carbide article.
  • reaction-bonded silicon carbide products have properties which are not uniform throughout the article. They either have very good abrasion resistance until the "skin" wears through or have marginal abrasion resistance throughout the article.
  • reaction-bonded silicon carbide products offer relatively poor oxidation resistance in that the abrasion resistance of the product rapidly deteriorates upon exposure of the product to oxidizing conditions at elevated temperatures.
  • the ideal wear-resistant refractory article should first have superior abrasion resistance.
  • the abrasion resistance should remain high even when the article is exposed for a prolonged period of time to oxidizing conditions at elevated temperatures.
  • the abrasion resistance of the article should be high, not only within the surface skin, but throughout the material. Indeed, uniformity in both chemical composition and physical properties throughout the refractory article, regardless of its size or shape, is a long sought, but seldom attained goal.
  • reaction-bonded silicon carbide products having good abrasion resistance
  • the abrasion resistance has often been confined to the surface of an article, or the abrasion resistance has deteriorated dramatically upon exposure of the article to oxidizing conditions, especially at high temperature.
  • reaction-bonded silicon carbide products having superior properties which can be produced at reasonable cost using commercially available raw materials.
  • reaction-bonded silicon carbide refractory article which has abrasion resistance superior to that of benchmark currently available materials.
  • a further objective is the provision of such an article in which the abrasion resistance remains high throughout the bulk of the article. It is a still further objective to provide such an abrasion resistant article which also exhibits very good oxidation resistance. It is also an objective of this invention to provide a reaction-bonded silicon carbide refractory article in which the composition and properties are more uniform throughout than exhibited by benchmark currently available materials.
  • this invention provides a silicon carbide refractory article which is reaction-bonded, the silicon carbide phase comprising about 65 wt % to about 85 wt % of the refractory, the bond phase comprising about 35 wt % to about 15 wt % of the refractory, respectively, the bond phase containing appreciable amounts of both silicon oxynitride and alumina.
  • An "appreciable amount” means at least about 30 wt % of the bond phase in the context of this application, and the term silicon oxynitride, as employed herein, contemplates a mixture of silicon oxynitride and O-'-SiAlON.
  • the reaction-bonded silicon carbide refractory article of this invention is produced from a raw batch containing solids and a vehicle.
  • the vehicle allows the raw batch to be molded into a green body with a desired shape but is substantially removed from the green body when it is subsequently dried and then fired and is not present in the final reaction-bonded article.
  • the raw batch solids comprise at least about 5 wt % silicon, at least about 5 wt % alumina, and at least about 1 wt % silica, the balance being silicon carbide.
  • the vehicle is added to the solids in sufficient type and quantity to yield a raw batch which can be molded using standard techniques.
  • the raw batch contains between about 1.5 wt % and about 12 wt % vehicle, most of which can be water in certain embodiments of the invention.
  • FIG. 1 is a graph showing the abrasion resistance of the fired surfaces of a reaction-bonded silicon carbide article of this invention and a benchmark reaction-bonded silicon carbide article of the prior art.
  • FIG. 2 is a graph showing the abrasion resistance of the surfaces of core samples cut from a reaction-bonded silicon carbide article of this invention and a benchmark reaction-bonded silicon carbide article of the prior art.
  • the raw batch from which the reaction-bonded silicon carbide refractory article of this invention is prepared comprises solids and a vehicle.
  • the solids generally will comprise between about 88 wt % and about 98.5 wt % of the raw batch, the vehicle between about 12 wt % and about 1.5 wt %, respectively.
  • the particle sizes of the solid components should be fine enough so that flowability of the raw batch is ensured and the intended chemical reactions take place at elevated firing temperatures.
  • the raw batch includes silicon carbide as the principle component.
  • the silicon carbide comprises between about 60 wt % and about 85 wt % of the raw batch solids, preferably between about 65 wt % and about 80 wt %.
  • Either the alpha or the beta silicon carbide polymorph, or mixtures thereof, can be employed and is available in commerce.
  • ⁇ -silicon carbide has relatively poor oxidation resistance compared with the alpha form.
  • the alpha polymorph is generally preferred over the beta for that reason and also because of its lower cost.
  • a mixture of silicon carbide grains having different particle sizes is preferably utilized. This facilitates particle packing, thereby reducing porosity and increasing the abrasion resistance of the reaction-bonded product.
  • none of the silicon carbide grain should exceed about 5 mm in size (4 mesh, U.S. Standard Sieve); preferably, the silicon carbide should not exceed about 3.4 mm in size (6 mesh, U.S. Standard Sieve). If larger grain is present, it will tend to settle out of the raw batch and lead to a product which is not homogeneous, especially if the vehicle content of the raw batch is toward the high end of the stated range.
  • the raw batch solids also contain fine silicon metal, between about 5 wt % and about 16 wt %, preferably between about 7 wt % and about 14 wt %, being present in the raw batch solids. Particle sizes in the range of about 74 micrometers (200 mesh U.S. Standard Sieve) and finer can be utilized.
  • the raw batch also contains a source of aluminum.
  • Alumina either the reactive alumina of high surface area or alumina of lower surface area can be employed. Reactive alumina having a surface area of at least about 2 m 2 /g is preferred.
  • the alumina will comprise between about 5 wt % and about 14 wt % of the raw batch solids, preferably between about 8 wt % and about 11 wt %.
  • the use of alumina, rather than another aluminum source, such as the metal is believed to advantageously affect the properties of the raw batch and the refractory articles produced therefrom.
  • aluminum metal is used as an aluminum source, for example, there is a reaction between the aluminum and an aqueous vehicle, even at room temperature, which yields a gas. The presence of this gas can prove to be troublesome in commercial processes; the gas leads to voids in the product, lower product density, and less than optimum abrasion resistance, for example.
  • Silica comprises between about 1 wt % and about 7 wt % of the raw batch solids, preferably between about 2 wt % and about 4 wt %.
  • the silica is preferably "fume" silica which is amorphous and available, for example, as "Microsilica EMS" of fine particle size having a surface area of 20-24 m 2 /g from Elken Corp., Pittsburgh, Pa.
  • the use of silica, in addition to silicon metal, as the source of silicon is believed to favorably affect the course of the nitridation reaction, as well as fabrication of the refractory articles of this invention.
  • the raw batch also comprises between about 1.5 wt % and about 12 wt % vehicle, depending upon whether the raw batch is intended to be cast, poured into a mold, pressed, or extruded, techniques for shaping a green body which are well known to those skilled in the art.
  • the raw batch can include water and can also contain various additives in small amounts. Such additives include, for example, binders, surfactants, deflocculants and small amounts of acid or base to regulate the pH.
  • a preferred deflocculant is DARVAN brand sodium polyelectrolyte, sold by R. T. Vanderbilt Co., Norwalk, Conn.
  • an aqueous vehicle constituting between about 4 wt % and about 7 wt % of the raw batch, preferably about 5 wt % of the raw batch. Greater amounts of the aqueous vehicle can be employed if the raw batch is to be poured into a mold.
  • a temporary binder will generally be present and can constitute between about 2 wt % and about 7 wt % of the raw batch, preferably about 4 wt % of the raw batch. Suitable temporary binders are well known to those skilled in the art and include lignone, dextrin and poly(vinyl alcohol), for example.
  • the raw batch solids and the vehicle are blended together in a mixer, such as is available from Hobart Corp., for example.
  • a mixer such as is available from Hobart Corp., for example.
  • the raw batch can be cast, poured or pressed into a plaster mold or a non-porous mold.
  • the resultant green body is removed from the mold, dried and then fired at one or more temperatures within the range of about 1300° C. to about 1500° C., e.g., at about 1400° C., which is well below the sintering temperature of silicon carbide, for that period of time necessary to form the bond phase, up to about 50 hours in some cases.
  • the oxidation resistance of the reaction-bonded silicon carbide article is measured by determining the increase in weight and volume of a standard size sample exposed to superheated steam for a prescribed period of time in accordance with ASTM C-863-77, entitled "Standard Recommended Practice for Evaluating Oxidation Resistance of Silicon Carbide Refractories at Elevated Temperatures".
  • the bending resistance, also called the modulus of rupture, of the reaction-bonded article can be determined by the threepoint method specified in ASTM C-133-81, entitled “Tests for Cold Crush Strength and Modulus of Rupture of Refractory Brick and Shapes".
  • the density and porosity of the reaction-bonded article are determined by methods well known to those skilled in the art.
  • the chemical and phase compositions of the various components of the reaction-bonded refractory article are determined by chemical and X-ray diffraction analysis.
  • a raw batch containing the following solids is prepared:
  • the raw batch solids are combined with a vehicle which comprises 5 parts by weight water and 0.1 part by weight Darvan brand deflocculant per 100 parts by weight solids.
  • a plaster mold having openings of 9 inches ⁇ 4.5 inches ⁇ 1 inch is filled with the raw batch mixture.
  • a cast green body with the aforestated dimensions is removed from the mold and dried. The green body is then fired in the muffle of a gas-fired kiln under a nitrogen atmosphere at 1400° C. for about 12 hrs. and subsequently allowed to cool to room temperature.
  • the reaction-bonded silicon carbide article of Example 1 is sectioned perpendicular to the 1 in. (25 mm) dimension with a diamond saw into two surface and three core fractions about 5 cm ⁇ 5 cm ⁇ ⁇ 4-5 mm thick for testing.
  • the as-fired surfaces of the two surface sections, as well as the as-fired surface of a CAST REFRAX® 3349 refractory sample are subjected to the abrasion resistance test based on ASTM G-76-83 described above. The results appear in FIG. 1.
  • the Standard Erosion Test results are about 70 mg weight loss from the CAST REFRAX 3349 refractory material, but only about 40 mg weight loss from the refractory article of this invention.
  • samples of the refractory article of Ex. 1 and CAST REFRAX 3349 refractory increased in volume by 2-3 % and >15%, respectively.
  • the uniformity of the properties of the refractory article of Ex. 1, compared against the benchmark CAST REFRAX® 3349 refractory material, is illustrated in the abrasion resistance tests of FIGS. 1 and 2 and in other studies.
  • the densities of the fired surface sections and core sections of the refractory article of Ex. 1 vary in the narrow range between 2.78 and 2 8 g/cm 3
  • surface and core sections of CAST REFRAX 3349 refractory vary in density from 2.5 to 2.7 g/cm 3
  • the bond phase in both the surface and core sections of the refractory article of Ex. 1 is found to contain appreciable amounts, i.e., at least about 30 wt %, of both silicon oxynitride and alumina.
  • the surface sections also contain a significant amount of sialon.
  • the free silicon contents of the five sections of the refractory article of this invention are all in the narrow range between 0.19 wt % and 0.21 wt %.
  • the free silicon contents in similar sections of CAST REFRAX 3349 refractory cover the broad range between 0.14 wt % to 2.59 wt %.
  • a pourable raw batch is prepared containing the following solids:
  • the raw batch solids are combined with a vehicle which comprises, per 100 parts solids by weight, 11.2 parts water and 0.1 part DARVAN brand deflocculant.
  • the raw batch is processed by pouring it into a plaster mold.
  • the resultant green body, which is 0.5 in. thick is dried and then fired as described in Example 1.
  • the reaction-bonded silicon carbide refractory article which is recovered after firing is found to have a density of 2.70 g/cm 3 , porosity of 11.5 vol %, and modulus of rupture (3-point) 12 Kpsi.
  • the modulus of rupture at 1350° C. is 8 Kpsi.
  • a raw batch intended to be shaped into a green body under pressure in a nonporous mold is prepared containing the following solids:
  • the raw batch solids are combined with a vehicle which comprises, per 100 parts solids by weight, 4.3 parts lignone and 1.8 parts water.
  • a vehicle which comprises, per 100 parts solids by weight, 4.3 parts lignone and 1.8 parts water.
  • the raw batch in a mold is pressed at 5 Kpsi into a green body which is dried and then fired as described in Example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)
  • Carbon And Carbon Compounds (AREA)
US08/306,087 1994-09-14 1994-09-14 Reaction-bonded silicon carbide refractory product Expired - Lifetime US5459112A (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
US08/306,087 US5459112A (en) 1994-09-14 1994-09-14 Reaction-bonded silicon carbide refractory product
US08/450,596 US5563108A (en) 1994-09-14 1995-05-25 Raw batch for producing reaction-bonded silicon carbide refractory product
US08/450,447 US5504046A (en) 1994-09-14 1995-05-25 Process for producing reaction-bonded silicon carbide refractory product
ZA957073A ZA957073B (en) 1994-09-14 1995-08-23 Reaction-bonded silicon carbide refractory product
EP95930968A EP0783467B1 (en) 1994-09-14 1995-08-28 Reaction-bonded silicon carbide refractory product
KR1019970700768A KR100386364B1 (ko) 1994-09-14 1995-08-28 반응결합된탄화규소내화물
DE69516703T DE69516703T2 (de) 1994-09-14 1995-08-28 Feuerfesterzeugnis aus reaktionsgebundenem siliziumcarbid
ES95930968T ES2148551T3 (es) 1994-09-14 1995-08-28 Producto refractario de carburo de silicio ligado por reaccion.
JP51020496A JP3311755B2 (ja) 1994-09-14 1995-08-28 反応結合型炭化ケイ素耐火物製品
AU34163/95A AU701442B2 (en) 1994-09-14 1995-08-28 Reaction-bonded silicon carbide refractory product
CA002199394A CA2199394A1 (en) 1994-09-14 1995-08-28 Reaction-bonded silicon carbide refractory product
DK95930968T DK0783467T3 (da) 1994-09-14 1995-08-28 Ildfast produkt af reaktionsbundet siliciumcarbid
BR9509007A BR9509007A (pt) 1994-09-14 1995-08-28 Artigo refratário de carboneto de silicio ligado por reação e cara básica e processo para produzir o artigo
PCT/US1995/010858 WO1996008450A1 (en) 1994-09-14 1995-08-28 Reaction-bonded silicon carbide refractory product
GR20000401784T GR3034089T3 (en) 1994-09-14 2000-08-02 Reaction-bonded silicon carbide refractory product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08/306,087 US5459112A (en) 1994-09-14 1994-09-14 Reaction-bonded silicon carbide refractory product

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US08/450,447 Division US5504046A (en) 1994-09-14 1995-05-25 Process for producing reaction-bonded silicon carbide refractory product
US08/450,596 Division US5563108A (en) 1994-09-14 1995-05-25 Raw batch for producing reaction-bonded silicon carbide refractory product

Publications (1)

Publication Number Publication Date
US5459112A true US5459112A (en) 1995-10-17

Family

ID=23183740

Family Applications (3)

Application Number Title Priority Date Filing Date
US08/306,087 Expired - Lifetime US5459112A (en) 1994-09-14 1994-09-14 Reaction-bonded silicon carbide refractory product
US08/450,447 Expired - Lifetime US5504046A (en) 1994-09-14 1995-05-25 Process for producing reaction-bonded silicon carbide refractory product
US08/450,596 Expired - Lifetime US5563108A (en) 1994-09-14 1995-05-25 Raw batch for producing reaction-bonded silicon carbide refractory product

Family Applications After (2)

Application Number Title Priority Date Filing Date
US08/450,447 Expired - Lifetime US5504046A (en) 1994-09-14 1995-05-25 Process for producing reaction-bonded silicon carbide refractory product
US08/450,596 Expired - Lifetime US5563108A (en) 1994-09-14 1995-05-25 Raw batch for producing reaction-bonded silicon carbide refractory product

Country Status (13)

Country Link
US (3) US5459112A (da)
EP (1) EP0783467B1 (da)
JP (1) JP3311755B2 (da)
KR (1) KR100386364B1 (da)
AU (1) AU701442B2 (da)
BR (1) BR9509007A (da)
CA (1) CA2199394A1 (da)
DE (1) DE69516703T2 (da)
DK (1) DK0783467T3 (da)
ES (1) ES2148551T3 (da)
GR (1) GR3034089T3 (da)
WO (1) WO1996008450A1 (da)
ZA (1) ZA957073B (da)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060281625A1 (en) * 2003-09-09 2006-12-14 Ngk Insulators, Ltd. Sic refractory comprising silicon nitride bond thereto and method for production thereof
US7446066B1 (en) * 2005-11-07 2008-11-04 Jai-Lin Sun Reverse reaction sintering of Si3N4/SiC composites
US20090169805A1 (en) * 2007-12-26 2009-07-02 Ngk Insulators, Ltd. Porous fired body and manufacturing method thereof
US20090312173A1 (en) * 2008-06-13 2009-12-17 Saint-Gobain Ceramics & Plastics, Inc. Volume-change resistant silicon oxy-nitride or silicon oxy-nitride and silicon nitride bonded silicon carbide refractory
CN101823892A (zh) * 2010-04-29 2010-09-08 河南科技大学 一种无水泥的原位氮化硅结合碳化硅预制件及制备方法
CN101565319B (zh) * 2009-06-10 2012-08-08 贾剑光 水泥窑预热器内筒用重结晶碳化硅挂板及制备方法
CN101565320B (zh) * 2009-06-10 2012-08-08 贾剑光 水泥窑预热器内筒用反应烧结碳化硅挂板及制备方法
CN101602607B (zh) * 2009-06-21 2012-11-21 贾剑光 水泥窑预热器用复合氮化物结合碳化硅挂板的烧制方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8379736B2 (en) * 2003-05-30 2013-02-19 Intellectual Ventures Holding 73 Llc Ultra-wideband communication system and method
US8097547B2 (en) * 2004-11-29 2012-01-17 Saint-Gobain Centre De Recherches Et D'etudes Europeen Sintered refactory material based on silicon carbide with a silicon nitride binder
EP2365949A2 (en) * 2009-07-07 2011-09-21 Morgan Advanced Materials And Technology Inc. Hard non-oxide or oxide ceramic / hard non-oxide or oxide ceramic composite hybrid article
WO2024038720A1 (ja) * 2022-08-19 2024-02-22 日本碍子株式会社 耐火物

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2618565A (en) * 1948-02-26 1952-11-18 Carborundum Co Manufacture of silicon nitride-bonded articles
US2636828A (en) * 1948-02-26 1953-04-28 Carborundum Co Silicon nitride-bonded refractory oxide bodies and method of making
US2752258A (en) * 1955-03-02 1956-06-26 Carborundum Co Silicon nitride-bonded silicon carbide refractories
US3206318A (en) * 1961-04-25 1965-09-14 Showa Denko Kk Refractory material
US3321321A (en) * 1964-02-13 1967-05-23 Lonza Werke Elektrochemische Fired refractory shape and process for its manufacture
US3991166A (en) * 1972-01-11 1976-11-09 Joseph Lucas (Industries) Limited Ceramic materials
US4113503A (en) * 1976-06-03 1978-09-12 Lucas Industries Limited Method of forming a ceramic product
US4230497A (en) * 1978-03-03 1980-10-28 Elektroschmelzwerk Kempten Gmbh Dense sintered shaped articles of polycrystalline α-silicon carbide and process for their manufacture
US4243621A (en) * 1977-09-28 1981-01-06 Toshiba Ceramics Co., Ltd. β'-Sialon sintered body and a method for manufacturing the same
US4476234A (en) * 1983-08-12 1984-10-09 Norton Company Refractory cement
US4506021A (en) * 1983-02-26 1985-03-19 Lucas Cookson Syalon Limited 0'-Phase sialon ceramic product and a method of forming dense ceramic product
US4587363A (en) * 1983-08-10 1986-05-06 Basf Aktiengesellschaft Continuous preparation of oxygen-containing compounds
US4800181A (en) * 1987-09-01 1989-01-24 Combustion Engineering, Inc. Silicon carbide refractory composition
US4826791A (en) * 1987-05-29 1989-05-02 Kennametal Inc. Silicon carbide-alpha prime sialon beta prime sialon
US4935389A (en) * 1988-05-30 1990-06-19 Nkk Corporation High strength high oxidation-resistance sialon sintered body
US4990469A (en) * 1987-11-23 1991-02-05 Norton Gmbh Refractory material and process for production of the same
JPH04114969A (ja) * 1990-08-31 1992-04-15 Ngk Insulators Ltd 窒化物結合ＳｉＣ耐火物
US5132257A (en) * 1987-03-16 1992-07-21 Hitachi, Ltd. Composite ceramic sintered body and process for production thereof
US5212123A (en) * 1990-10-24 1993-05-18 Savoie Refractaires Refractory materials formed from refractory grains bonded by a sialon matrix containing dispersed graphite and/or boron nitride particles and a process for the preparation of these materials
US5302329A (en) * 1989-04-28 1994-04-12 Nihon Cement Co., Ltd. Process for producing β-sialon based sintered bodies
US5316988A (en) * 1993-08-02 1994-05-31 Eg&G Idaho, Inc. Sialon ceramic compositions and methods of fabrication
US5336280A (en) * 1991-04-15 1994-08-09 Pechiney Electrometallurgie Abrasive and/or refractory products based on melted and solidified oxynitrides and process preparing the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4578363A (en) * 1984-01-23 1986-03-25 Kennecott Corporation Silicon carbide refractories having modified silicon nitride bond

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2618565A (en) * 1948-02-26 1952-11-18 Carborundum Co Manufacture of silicon nitride-bonded articles
US2636828A (en) * 1948-02-26 1953-04-28 Carborundum Co Silicon nitride-bonded refractory oxide bodies and method of making
US2752258A (en) * 1955-03-02 1956-06-26 Carborundum Co Silicon nitride-bonded silicon carbide refractories
US3206318A (en) * 1961-04-25 1965-09-14 Showa Denko Kk Refractory material
US3321321A (en) * 1964-02-13 1967-05-23 Lonza Werke Elektrochemische Fired refractory shape and process for its manufacture
US3991166A (en) * 1972-01-11 1976-11-09 Joseph Lucas (Industries) Limited Ceramic materials
US4113503A (en) * 1976-06-03 1978-09-12 Lucas Industries Limited Method of forming a ceramic product
US4243621A (en) * 1977-09-28 1981-01-06 Toshiba Ceramics Co., Ltd. β'-Sialon sintered body and a method for manufacturing the same
US4230497A (en) * 1978-03-03 1980-10-28 Elektroschmelzwerk Kempten Gmbh Dense sintered shaped articles of polycrystalline α-silicon carbide and process for their manufacture
US4506021A (en) * 1983-02-26 1985-03-19 Lucas Cookson Syalon Limited 0'-Phase sialon ceramic product and a method of forming dense ceramic product
US4587363A (en) * 1983-08-10 1986-05-06 Basf Aktiengesellschaft Continuous preparation of oxygen-containing compounds
US4476234A (en) * 1983-08-12 1984-10-09 Norton Company Refractory cement
US5132257A (en) * 1987-03-16 1992-07-21 Hitachi, Ltd. Composite ceramic sintered body and process for production thereof
US4826791A (en) * 1987-05-29 1989-05-02 Kennametal Inc. Silicon carbide-alpha prime sialon beta prime sialon
US4800181A (en) * 1987-09-01 1989-01-24 Combustion Engineering, Inc. Silicon carbide refractory composition
US4990469A (en) * 1987-11-23 1991-02-05 Norton Gmbh Refractory material and process for production of the same
US4935389A (en) * 1988-05-30 1990-06-19 Nkk Corporation High strength high oxidation-resistance sialon sintered body
US5302329A (en) * 1989-04-28 1994-04-12 Nihon Cement Co., Ltd. Process for producing β-sialon based sintered bodies
JPH04114969A (ja) * 1990-08-31 1992-04-15 Ngk Insulators Ltd 窒化物結合ＳｉＣ耐火物
US5212123A (en) * 1990-10-24 1993-05-18 Savoie Refractaires Refractory materials formed from refractory grains bonded by a sialon matrix containing dispersed graphite and/or boron nitride particles and a process for the preparation of these materials
US5336280A (en) * 1991-04-15 1994-08-09 Pechiney Electrometallurgie Abrasive and/or refractory products based on melted and solidified oxynitrides and process preparing the same
US5316988A (en) * 1993-08-02 1994-05-31 Eg&G Idaho, Inc. Sialon ceramic compositions and methods of fabrication

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7494949B2 (en) * 2003-09-09 2009-02-24 Ngk Insulators, Ltd. SiC refractory comprising silicon nitride bond thereto and method for production thereof
US20060281625A1 (en) * 2003-09-09 2006-12-14 Ngk Insulators, Ltd. Sic refractory comprising silicon nitride bond thereto and method for production thereof
US7446066B1 (en) * 2005-11-07 2008-11-04 Jai-Lin Sun Reverse reaction sintering of Si3N4/SiC composites
US20090169805A1 (en) * 2007-12-26 2009-07-02 Ngk Insulators, Ltd. Porous fired body and manufacturing method thereof
EP2085369A1 (en) * 2007-12-26 2009-08-05 Ngk Insulator, Ltd. Porous fired body and manufacturing method thereof
US8101269B2 (en) 2007-12-26 2012-01-24 Ngk Insulators, Ltd. Porous fired body and manufacturing method thereof
US20090312173A1 (en) * 2008-06-13 2009-12-17 Saint-Gobain Ceramics & Plastics, Inc. Volume-change resistant silicon oxy-nitride or silicon oxy-nitride and silicon nitride bonded silicon carbide refractory
US8003557B2 (en) 2008-06-13 2011-08-23 Saint-Gobain Ceramics & Plastics, Inc. Volume-change resistant silicon oxy-nitride or silicon oxy-nitride and silicon nitride bonded silicon carbide refractory
CN101565320B (zh) * 2009-06-10 2012-08-08 贾剑光 水泥窑预热器内筒用反应烧结碳化硅挂板及制备方法
CN101565319B (zh) * 2009-06-10 2012-08-08 贾剑光 水泥窑预热器内筒用重结晶碳化硅挂板及制备方法
CN101602607B (zh) * 2009-06-21 2012-11-21 贾剑光 水泥窑预热器用复合氮化物结合碳化硅挂板的烧制方法
CN101823892A (zh) * 2010-04-29 2010-09-08 河南科技大学 一种无水泥的原位氮化硅结合碳化硅预制件及制备方法
CN101823892B (zh) * 2010-04-29 2012-08-08 河南科技大学 一种无水泥的原位氮化硅结合碳化硅预制件及制备方法

Also Published As

Publication number Publication date
ZA957073B (en) 1996-04-15
ES2148551T3 (es) 2000-10-16
DE69516703D1 (de) 2000-06-08
EP0783467A1 (en) 1997-07-16
AU3416395A (en) 1996-03-29
KR970704644A (ko) 1997-09-06
KR100386364B1 (ko) 2003-08-19
AU701442B2 (en) 1999-01-28
EP0783467A4 (en) 1997-09-24
GR3034089T3 (en) 2000-11-30
JP3311755B2 (ja) 2002-08-05
EP0783467B1 (en) 2000-05-03
JPH10500095A (ja) 1998-01-06
DE69516703T2 (de) 2000-12-28
DK0783467T3 (da) 2000-10-02
WO1996008450A1 (en) 1996-03-21
US5504046A (en) 1996-04-02
CA2199394A1 (en) 1996-03-21
US5563108A (en) 1996-10-08
BR9509007A (pt) 1997-10-14

Similar Documents

Publication Publication Date Title
US2618565A (en) Manufacture of silicon nitride-bonded articles
US5521129A (en) Sialon-bonded silicon carbide refractory
US4885264A (en) Pressure-sintered polycpystalline mixed materials with a base of hexagonal boron nitride, oxides and carbides
EP0153000B1 (en) Refractories of silicon carbide and related materials having a modified silicon nitride bonding phase
JPH027908B2 (da)
JPS6048474B2 (ja) 窒化ケイ素焼結体及びその製法
US5459112A (en) Reaction-bonded silicon carbide refractory product
JPH07277814A (ja) アルミナ基セラミックス焼結体
US4690790A (en) Silicon nitride/silicon carbide composition and articles thereof
US5308561A (en) Process for production of a Si3 N4, based material
US5804521A (en) Process for production of a silicon nitride ceramic
Lee et al. Effect of β–Si3N4 seed crystal on the microstructure and mechanical properties of sintered reaction-bonded silicon nitride
US5718866A (en) Process for producing refractory materials
JPS6212663A (ja) Ｂ４ｃ質複合体およびその製造方法
JPH03261611A (ja) 窒化けい素複合粉末の製造方法
JP2004256339A (ja) 窒化珪素質焼結体の製造方法
KR940010097B1 (ko) 질화 규소가 결합된 탄화 규소 내화물질
JP2696734B2 (ja) 窒化珪素質焼結体の製造法
JP2742620B2 (ja) 硼化物―酸化アルミニウム質焼結体およびその製造方法
EP0317147B1 (en) Si3n4-al2o3 composite sintered bodies and method of producing the same
JPH06305840A (ja) 窒化珪素質焼結体及びその製造方法
JPH02233560A (ja) 高強度サイアロン基焼結体
JPH02221160A (ja) 高密度窒化けい素質焼結体の製造方法
JPS6126566A (ja) ＳｉＣ質複合体の焼結方法
JPH0324430B2 (da)

Legal Events

Date Code Title Description
AS Assignment

Owner name: CARBORUNDUM COMPANY, THE, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KIM, BAEK H.;REEL/FRAME:007159/0183

Effective date: 19940825

STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12